CN1266837A - Process for producing fluoroalcohol - Google Patents

Process for producing fluoroalcohol Download PDF

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Publication number
CN1266837A
CN1266837A CN99119467A CN99119467A CN1266837A CN 1266837 A CN1266837 A CN 1266837A CN 99119467 A CN99119467 A CN 99119467A CN 99119467 A CN99119467 A CN 99119467A CN 1266837 A CN1266837 A CN 1266837A
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fluorinated alcohols
residual initiators
alkali
decomposition
reaction mixture
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CN99119467A
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CN1122653C (en
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山口史彦
高木祥二
吉沢透
小仓英嗣
胜部俊之
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for producing a fluoroalcohol of the following formula (1)(n=1 or 2, wherein R1 represents F or CF3 when n=1; R1 represents F when n=2) comprising reacting methanol with tetrafluoroethylene or hexafluoropropylene in the presence of an initiator wherein the fluoroalcohol of formula (1) is distilled after decomposing the remaining initiator contained in the reaction mixture.

Description

The method for preparing fluorinated alcohols
The present invention relates to the method for preparation by the fluorinated alcohols of general formula (1) expression:
H(CFR 1CF 2) nCH 2OH (1)
N=1 or 2 wherein; When n=1, R 1Represent F or CF 3When n=2, R 1Represent F.
Relevant preparation H (CF 2CF 2) nCH 2The technology of OH (n=1 or 2) discloses in open No.154707/1979 of Japanese unexamined patent and U.S. Patent No. 2,559,628 and has contained H (CF 2CF 2) nCH 2The mixture of the telomer of OH (n maximum value=12) can make by methyl alcohol and tetrafluoroethylene are reacted in the presence of tertiary butyl octyl group superoxide.
But,, still have the evaporation residue of about hundreds of ppm order of magnitude not remove even carry out purifying by distillation with the mixture of the telomer that this method obtained.When its preparation comprise substrate and the process of the information recording carrier of a kind of recording layer that is suitable for laser-light write and/or reads of on described substrate, setting up such as CD-R and DVD-R in when being used as solvent, disadvantageous situation can appear inevitably, promptly, because the influence of said evaporation residue, high-quality information recording carrier then can't obtain.
An object of the present invention is to provide a kind of method that is prepared as follows the fluorinated alcohols shown in the general formula (1),
H(CFR 1CF 2) nCH 2OH (1)
(wherein n and R 1As hereinbefore defined), said fluorinated alcohols is substantially free of impurity such as evaporation residue and ultraviolet radiation absorption material.
The contriver finds: after by decomposition the residual initiators in the reaction mixture being removed, the fluorinated alcohols as general formula (1) shown in is distilled, above-mentioned purpose just can realize.The present invention finishes with regard to being based on this new discovery.
The present invention relates to following method:
1. method for preparing the fluorinated alcohols of following general formula (1) expression:
H(CFR 1CF 2) nCH 2OH (1)
N=1 or 2 wherein, when n=1, R 1Represent F or CF 3When n=2, R 1Represent F; This method comprises reacts methyl alcohol and tetrafluoroethylene or R 1216 in the presence of initiator, after contained residual initiators decomposes in reaction mixture, the fluorinated alcohols shown in the formula (1) is distilled.
2. according to the 1st described method for preparing fluorinated alcohols above, wherein at least a the carrying out that is selected from the following manner adopted in the decomposition of described residual initiators: described residual initiators is decomposed, by contacting with acid catalyst described residual initiators decomposed, by contacting with reductive agent described residual initiators decomposed, described residual initiators decomposed and by contacting with alkali described residual initiators decomposition by the UV radiation by the reacting by heating mixture.
3. according to the 1st described method for preparing fluorinated alcohols above, the distillate that wherein will contain fluorinated alcohols shown in the formula (1) contacts further distillation of back with alkali in the presence of alkali or with described distillate.
In the reaction of the reaction of methyl alcohol and tetrafluoroethylene or R 1216 in the presence of initiator, use methyl alcohol with the amount that is in excess in tetrafluoroethylene or R 1216.Temperature of reaction is about 40～140 ℃, and the reaction times is about 3～12 hours, and reaction pressure is about 0.2～1.2MPa.This reaction can be carried out in high-pressure reactor, as carrying out in autoclave.Preferably this reaction system is cleaned with rare gas elementes such as nitrogen or argon gas.Described reaction is carried out usually in batches.
The example of initiator comprises superoxide and azo-compound.Preferably use and under temperature of reaction, have about 0.5-10 initiator of hour transformation period.
Preferred initiator comprises: ditertiary butyl peroxide (can trade(brand)name " butyl D excessively " obtain, NOF company produces), tert-butyl hydroperoxide-2-ethylhexanoate (can trade(brand)name " butyl O excessively " obtain, NOF company product), tert-butyl hydroperoxide sec.-propyl carbonic ether (can trade(brand)name " butyl I excessively " obtain, NOF company produces) and similarly superoxide; And Diisopropyl azodicarboxylate, the two cyclohexanenitriles of azo and similar azo-compound.
Based on every mol of tetrafluoroethylene or R 1216, can use about 0.005～0.1 mole initiator usually.
Above-mentioned reaction can be carried out in the presence of acid acceptor.The example of described acid acceptor comprises: the carbonate and the supercarbonate of lime carbonate, magnesiumcarbonate, yellow soda ash, salt of wormwood, barium carbonate, sodium bicarbonate, saleratus and similar basic metal or alkaline-earth metal; Calcium oxide, calcium hydroxide and soda-lime.Preferred acid acceptor is the strong alkaline substance that can be captured in formed acid (as HF) in the reaction process and don't damaging reaction mixture.
Usage quantity to acid acceptor does not limit especially, but based on every mol of tetrafluoroethylene or R 1216, can use about 0.001～0.1 mole acid acceptor.
The present invention randomly is included in any excessive methyl alcohol is removed in reaction after finishing from reaction mixture distilation steps.
To being used for the mode of the undecomposed decomposition of initiator of reaction mixture is had no particular limits, the example of described mode includes, but is not limited to following (i)-(v).
Following (ii), (iii) and (v), " contact " finished by acid catalyst, reductive agent or alkali are added in the reaction mixture.
(i) decomposition of being undertaken by heating
The temperature of reacting by heating mixture can suitably be selected according to the kind of used initiator, but is generally about 100-200 ℃.Perhaps in open system, carry out or in the system of sealing, heated about 0.5-10 hour.
(ii) by contacting the decomposition of carrying out with acid catalyst
Described acid catalyst can be mineral acid, organic acid or solid acid catalyst.
The example of mineral acid comprises sulfuric acid, hydrochloric acid, nitric acid, hydroiodic acid HI and Hydrogen bromide.The organic acid example comprises acetate and trifluoromethanesulfonic acid.The example of solid acid catalyst comprises silica-alumina catalyst, silica-magnesia catalyst and has the ion exchange resin or the ion-exchange membrane of sulfo group, carboxyl and similar acidic-group.The preferred example of ion-exchange membrane is NAFION (trade mark, the product of E.I.DuPont de Nemours and Company is a kind of perfluorinated sulfonic acid ionomer).
These acid catalysts can be used singly or in combination.
The consumption of described acid catalyst can suitably be selected according to amount that joins the initiator in the reaction system and reaction conditions, but with respect to the initiator of added per 100 weight parts, the consumption of acid catalyst is generally about 1-500 weight part.
Decomposing the condition of described residual initiators can suitably be selected according to the kind of used initiator and acid catalyst by acid catalyst.Decomposition that should be by acid catalyst in the system of an open system or a sealing under about 0-100 ℃ about 0.5-20 hour usually.
(iii) by contacting the decomposition of carrying out with reductive agent
The example of reductive agent comprises the salt of Fe (II) salt, Cr (II) salt, Cu (I) or Cu (II) salt, Ag (I) salt and similar transition metal, and thiosulphate.That can mention specifically, has a FeSO 4, CrCl 2, CuCl, Cu (OCOCH 3) 2, [Ag (NH 3) 2] OH and NaS 2O 3These reductive agents can be used singly or in combination.
The consumption of described reductive agent can suitably be selected according to amount that joins the initiator in the reaction system and reaction conditions, but with respect to added every mole of initiator, the consumption of reductive agent is generally about 0.001-5 mole.
Decomposing the condition of described residual initiators can suitably be selected according to the kind of used initiator and reductive agent by reductive agent.Decomposition that should be by reductive agent in the system of an open system or a sealing under about 20-100 ℃ about 0.5-10 hour usually.
The (iv) decomposition of being undertaken by the UV radiation
Can carry out described UV decomposition in about 0.5-10 hour by reaction mixture being shone with UV (UV-light, about 100-390nm).Can suitably select with the wavelength of UV irradiation according to the kind of used initiator.This UV irradiation can be undertaken by adopting (for example) ultrahigh pressure mercury lamp, high voltage mercury lamp, medium pressure mercury lamp or low pressure mercury lamp.
(v) by contacting the decomposition of carrying out with alkali
The example of alkali comprises: yellow soda ash, salt of wormwood and similar alkaline carbonate; Sodium bicarbonate, saleratus and similar alkali metal hydrocarbonate; Sodium methylate, sodium ethylate, sodium propylate, potassium tert.-butoxide, lithium ethoxide and similar alkali metal alcoholates; Sodium hydroxide, potassium hydroxide, lithium hydroxide and similar alkali metal hydroxide; Calcium hydroxide, hydrated barta, magnesium hydroxide and similar alkaline earth metal hydroxides; Aluminium hydroxide and soda-lime.
These alkali can be used singly or in combination.
The consumption of described alkali can suitably be selected according to amount that joins the initiator in the reaction system and reaction conditions, but with respect to added every mole of initiator, the consumption of alkali is generally about 0.001-5 mole.
Decomposing the condition of described residual initiators can suitably be selected according to the kind of used initiator and alkali by alkali.
The decomposition that should be undertaken by alkali in the system of an open system or a sealing under about 20-100 ℃ about 0.5-10 hour usually.
In addition, the distillation of fluorinated alcohols shown in the mutual-through type (1) can be carried out after adding alkali immediately.
When implementing decomposition to residual initiators with contacting of alkali, the amount that is included in the impurity in the fluorinated alcohols shown in general formula (1) is lowered to very low degree, need not by in the presence of alkali or after the distillate that contains formula (1) fluorinated alcohols contacts with alkali it further being distilled.Described " further distillation " addressed hereinafter.
Decomposition to residual initiators can be carried out in batches or carry out continuously.
The aforesaid way that decomposes residual initiators can two or more the mode of combination use.
In the process of decomposing residual initiators according to the present invention, preferably described residual initiators is decomposed fully; But after this processing,, be preferably about 50 ppm by weight or following as long as the concentration of the residual initiators in the reaction mixture reaches about 1000 ppm by weight or following just enough.The concentration of residual initiators is based on the total amount of the reaction mixture that comprises excessive methanol and calculates.
After described residual initiators is decomposed, with general formula (1) H (CFR 1CF 2) nCH 2OH (n and R 1Fluorinated alcohols as hereinbefore defined) is carried out distillation purifying,, will be present in other impurity in the reaction mixture such as methyl alcohol, H (CF that is 2CF 2) nCH 2OH (n 〉=3) and H (CF (CF 3) CF 2) nCH 2OH (n 〉=2) removes.
Distillation purifying can carry out in batches or carry out continuously.
In the method for the invention, after having finished above-mentioned distillation purifying, can be to purified as general formula (1) H (CFR 1CF 2) nCH 2OH (n and R 1Fluorinated alcohols as hereinbefore defined) promptly, contains distillate further distillation in the presence of alkali or after described effluent liquid is contacted with alkali of fluorinated alcohols shown in the formula (1).The example of the alkali that can join in the above-mentioned fluorinated alcohols distillate or contact with it is included in above (those alkali of mentioning v).For every kilogram of distillate that contains fluorinated alcohols shown in the general formula (1), the consumption of described alkali is about 0.05-1.0 mole, is preferably about 0.1-0.5 mole.
To the distillation of above-mentioned distillate can in the presence of the alkali or described effluent liquid with carry out in batches or continuously after alkali contacts.
According to method of the present invention, can obtain the fluorinated alcohols shown in general formula (1), evaporation residue wherein is 50ppm or still less, preferred 25ppm or still less, more preferably 10ppm or still less.
The amount of evaporation residue can followingly be determined.At 40C, evaporation and to the resistates weighing under the condition of 5mmHg and is used based on the ppm by weight of fluorinated alcohols and is represented with fluorinated alcohols.
Be not higher than 0.1abs according to the fluorinated alcohols ultraviolet absorptivity at the 205nm place in methyl alcohol shown in the general formula (1) of the present invention's acquisition, be preferably-0.1abs or lower, more preferably-0.2abs or lower.Ultraviolet absorptivity in methyl alcohol can use the mixture of the fluorinated alcohols of 1 milliliter of general formula (1) and 3 ml methanol as sample, and measures as object of reference with methyl alcohol.
The fluorinated alcohols amount of the resistates after (i) fluorinated alcohols is evaporated that is meant in fact free from foreign meter that makes according to the present invention is not higher than 50ppm, preferably is not higher than 25ppm, more preferably no higher than 10ppm; And/or (ii) its ultraviolet (205nm) optical density in methyl alcohol is not higher than 0.1abs, preferably is not higher than-0.1abs, more preferably no higher than-0.2abs.
The information recording carrier that contains substrate and be based upon a kind of recording layer that is suitable for laser-light write and/or reads on the described substrate, can be by dyestuff being dissolved in a kind of solvent that contains according to the fluorinated alcohols shown in the general formula of the present invention (1), be preferably dissolved in and contain the containing in the fluorous solvent of said fluorinated alcohols, then use the dye solution of gained, carry out a series of routine operation again, comprise and use resulting dye solution coated substrate and will this coated drying substrates and obtain a kind ofly to contain the recording layer of dyestuff and make.The example of above-mentioned dyestuff comprises cyanine dyes, phthalocyanine pigment, pyrylium dye, thiapyran dyestuff, squarylium dyestuff, Austria (azulenium) dyestuff, indophenol dye, indole aniline (indoaniline) dyestuff, triphenylmethane dye, quinone dyestuff, ammonium dyestuff, diimmonium dyestuff and metal complex dyes.The raw material that is used to prepare substrate comprises plastics such as polycarbonate, polymethylmethacrylate, Resins, epoxy, unbodied polyolefine, polyester and polyvinyl chloride, and glass and pottery.In order to improve surperficial slickness and viscosity or to prevent that recording layer from coming off, can between recording layer and substrate, apply one deck undercoat and/or can on recording layer, form layer protective layer.
According to the present invention, can easily make HCF in fact free from foreign meter 2CF 2CH 2OH, H (CF 2CF 2) 2CH 2OH and HCF (CF 3) CF 2CH 2OH, they be applicable to the recording layer that is suitable for laser-light write and/or reads that comprises substrate and make up thereon information recording carrier (CD such as CD-R, DVD-R etc.) manufacturing or be used for the manufacturing of the photochromics of film.
Implement best mode of the present invention
Following embodiment is to further detailed description of the present invention.Embodiment 1
Lime carbonate (30 gram) is joined in the autoclave.Atmosphere nitrogen replacement in the autoclave, and then aspirate nitrogen with vacuum pump.Join in the autoclave with methyl alcohol (2 liters), tetrafluoroethylene with as the ditertiary butyl peroxide (45 gram) of initiator.Make reaction mixture reaction 6 hours under 125 ℃ and 0.8MPa.(SE-30 3m) comes in the analyze reaction mixture concentration of remaining ditertiary butyl peroxide, and recording its value is 1.86% with gas-chromatography.After this, reaction mixture was stirred 3 hours down at 140 ℃, decompose with ditertiary butyl peroxide with remnants.Use once more gas chromatographic analysis the concentration of residual ditertiary butyl peroxide, find that its value is below detectability (10ppm).After the cooling, the reaction mixture distillation to remove methyl alcohol, is further distilled reaction mixture, then to separate H (CF from mixture 2CF 2) nCH 2OH (n be 2 or bigger integer) obtains HCF 2CF 2CH 2OH cut (1.2 liters).This gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 20ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
The comparative example 1
Repeat the step of embodiment 1, just reaction mixture was not stirred 3 hours down at 140 ℃.Gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 590ppm, and its ultraviolet absorptivity (205nm) is 2.0abs.
Embodiment 2
Replaced in 5 hours reaction mixture is stirred 3 hours down with residual initiators is decomposed at 140 ℃ except adding sulfuric acid (40 gram) and at room temperature reaction mixture being stirred, all the other repeat the step of embodiment 1.Gained HCF 2CF 2CF 2The evaporation residue substrate concentration of OH cut is 22ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 3
Except adding NAFION (135 gram) and replacing in 1.5 hours reaction mixture is stirred 3 hours down with residual initiators is decomposed at 140 ℃ under 70 ℃ reaction mixture being stirred, all the other repeat the step of embodiment 1.Gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 19ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 4
Except using tert-butyl hydroperoxide-2-ethylhexanoate (67 gram) to replace ditertiary butyl peroxide (45 gram) and using FeSO4 (94 gram) to replace H 2SO 4(40 gram) with outside under agitation residual initiators being decomposed, all the other repeat the step of embodiment 1.Gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 19ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 5
Except under the irradiation of high voltage mercury lamp (100W) reaction mixture being replaced reaction mixture is stirred 3 hours down with residual initiators is decomposed at 140 ℃ in 50 ℃ of stirrings in 4 hours, all the other repeat the step of embodiment 1.Gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 21ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 6
Replace FeSO except in reaction mixture, adding NaOH (27 gram) 4(94 gram) with outside residual initiators is under agitation decomposed, all the other repeat the step of embodiment 4.Gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 18ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 7
Repeat reaction among the embodiment 1, to the decomposition and the distillatory step of residual initiators.H (CF to gained 2CF 2) nCH 2OH (n be 2 or bigger integer) cut further distills and separates, and obtains H (CF 2CF 2) 2CH 2The OH cut.This gained H (CF 2CF 2) 2CH 2The evaporation residue substrate concentration of OH cut is 25ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 8
Except replacing with R 1216 the tetrafluoroethylene, all the other repeat the step of embodiment 1 react, to the decomposition and the distillation purifying of residual initiators.Gained HCF (CF 3) CF 2CH 2The evaporation residue substrate concentration of OH cut is 25ppm, and its ultraviolet absorptivity (205nm) is-1.0abs.
Embodiment 9
Except the sodium methylate (30 gram) of adding 28% in reaction mixture and to the reaction mixture distillation, all the other repeat the step of embodiment 1.Gained HCF 2CF 2CH 2The evaporation residue substrate concentration of OH cut is 10ppm, and its ultraviolet absorptivity (205nm) is-2.0abs.

Claims (3)

1. method for preparing the fluorinated alcohols of following general formula (1) expression:
H(CFR 1CF 2) nCH 2OH (1)
N=1 or 2 in the formula (1), when n=1, R 1Represent F or CF 3When n=2, R 1Represent F, this method comprises reacts methyl alcohol and tetrafluoroethylene or R 1216 in the presence of initiator, after wherein contained residual initiators decomposes in reaction mixture, the fluorinated alcohols shown in the formula (1) is distilled.
2. the method for preparing fluorinated alcohols as claimed in claim 1, wherein adopt at least a mode be selected from down group to carry out decomposition to described residual initiators: by the reacting by heating mixture with described residual initiators decomposes, by contact with acid catalyst with described residual initiators decompose, by contact with reductive agent with described residual initiators decompose, by the UV radiation with described residual initiators decomposition with by contacting with alkali with described residual initiators decomposition.
3. the method for preparing fluorinated alcohols as claimed in claim 1 wherein will contain distillate further distillation in the presence of alkali or after described distillate is being contacted with alkali of fluorinated alcohols shown in the formula (1).
CN99119467A 1999-03-15 1999-09-24 Process for producing fluoroalcohol Expired - Fee Related CN1122653C (en)

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JP68932/1999 1999-03-15
JP6893299 1999-03-15

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Publication number Priority date Publication date Assignee Title
JP3029618B1 (en) * 1998-12-28 2000-04-04 ダイキン工業株式会社 Manufacturing method of fluorine alcohol
EP1386903A1 (en) * 1999-08-20 2004-02-04 Asahi Glass Company, Limited Method for purifying a fluorinated hydroxyl compound
JP4599780B2 (en) * 2001-09-13 2010-12-15 ダイキン工業株式会社 Catalyst for producing fluorine-containing alcohol compound and method for producing fluorine-containing alcohol
US6992224B2 (en) * 2004-05-12 2006-01-31 Honeywell International Inc. Manufacture of fluorinated alcohols
CN1305825C (en) * 2005-03-16 2007-03-21 中昊晨光化工研究院 Purifying method for propanol tetrafluoride

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GB1430582A (en) 1972-01-14 1976-03-31 Haszeldine R N Preparation of fluorinated organic materials
IT1226574B (en) * 1988-08-02 1991-01-24 Ausimont Spa PROCESS FOR THE PREPARATION OF FLUORINATED COMPOUNDS AND NEW PRODUCTS OBTAINED.
DE4124807A1 (en) 1991-07-26 1993-01-28 Hoechst Ag METHOD FOR PRODUCING PRIMARY AND SECOND FLUORINE ALCOHOLS
JP3029618B1 (en) 1998-12-28 2000-04-04 ダイキン工業株式会社 Manufacturing method of fluorine alcohol

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US6187969B1 (en) 2001-02-13
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EP0968989A2 (en) 2000-01-05
RU2163230C1 (en) 2001-02-20

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